CN104011059A - Metal complex compounds as catalysts for polyurethane compositions - Google Patents

Metal complex compounds as catalysts for polyurethane compositions Download PDF

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CN104011059A
CN104011059A CN201280060785.0A CN201280060785A CN104011059A CN 104011059 A CN104011059 A CN 104011059A CN 201280060785 A CN201280060785 A CN 201280060785A CN 104011059 A CN104011059 A CN 104011059A
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metal complex
complex compounds
represent
salt
metallic cation
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CN104011059B (en
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U·布尔克哈德特
R·堪纳斯
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Sika Technology AG
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Sika Technology AG
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract

The invention relates to metal complex compounds of the formula Mk(L)x(Y)kz-nx, where the ligand L has the formula (I), and to metal complex compounds which comprise the reaction product of at least one salt or a complex of a transition metal or a main group metal element of the groups 13 to 15 and at least one 1,3-ketoamide. Such complex compounds are suitable in particular as catalysts for polyurethane compositions. The invention also relates to two-component polyurethane compositions comprising at least one polyisocyanate as the first component, at least one polyol as the second component, and at least one such metal complex compound as the catalyst. The invention additionally relates to different uses of said two-component polyurethane compositions

Description

As the metal complex compounds of the catalyzer for polyurethane composition
Technical field
The present invention relates to polyurethane composition and the field for the catalyzer of polyurethane composition.
Background technology
Polyurethane composition is long-term known and for many scopes.In academia, be conventionally divided into single component and bicomponent polyurethane composition.One-component polyurethane compositions solidifies under the impact of air moisture.Bicomponent polyurethane composition comprises the curing agent component as second component, and described curing agent component mainly comprises polyamines and/or polyvalent alcohol.All use in both cases compound or the prepolymer containing isocyanate groups.
Add catalyzer in order to accelerate to solidify.Although known a large amount of catalysts for polyurethanes, but most of catalysts for polyurethanes is being not especially optionally aspect urethane reaction (being the OH-group of alcohol and reacting of isocyanate groups), but also other reaction of catalysis isocyanate groups more or less, the formation of for example allophanate and the formation of biuret or ring trimerization.Especially, urethane reacts conventionally and the response competition of isocyanate groups and water, and the reaction of isocyanate groups and water causes urea groups and discharges gaseous carbon dioxide.For many polyurethane compositions, particularly for it as for the purposes of tackiness agent and sealing agent, coating or casting resin, described side reaction is interfering, because described side reaction causes bubble formation and therefore causes worse shape stability, more weak adhesivity, lower physical strength, unsatisfied outward appearance and the too low result reproduced when curing.Residual moisture content to the responsible water source of bubble formation from composition components (particularly polyvalent alcohol and filler), even if described composition is still moistening and conventionally have a residual moisture content of 0.01 to 0.5 % by weight more or less after drying process; Or be derived from ambient moisture, thereby described ambient moisture penetrates into composition by diffusion from air or base material, this for example, occurs especially in the case of high atmospheric moisture, porous substrate and/or hydrophilic polyvalent alcohol (polyether glycol often using in practice).In practice, normally used amine catalyst (for example tertiary amine) and tin catalyst (for example carboxylic acid dialkyl tin) often cause obvious bubble formation just.Residual moisture content in polyurethane composition also causes the responsive catalyzer (for example bismuth carboxylate) of hydrolysis inactivation when longer preservation (storage) before composition uses, and this adversely affects curing speed and mechanical property.In addition, for example, for some known catalyzer (carboxylic acid dialkyl tin), the tolerance deficiency through curing composition under thermal load, wherein catalyzer causes molecular weight and molecular weight, i.e. depolymerization, and loss physical strength.In addition, many known catalyzer at room temperature for solid and in urethane parent material or softening agent, be difficult to dissolve, make for the application in its composition at room temperature solidifying must be with an organic solvent.Finally, the catalyzer that some are known, particularly, based on heavy metal compound those, has toxicity risk.
US2010/0069575 disclose use do not have polyether structure unit simple function 1,3-keto-amide is as the inhibitor of the unsaturated polyester resin for copper (II) catalysis.US6,734,268 have described " the decomplexing agent " that use 1,3-keto-amide (conventionally also comprising polyether type) conduct to be used for the radical-cured tackiness agent (the particularly tackiness agent based on (methyl) acrylate) of metal-salt catalysis especially.As suitable metal-salt, mention the metal-salt that is derived from copper, vanadium, chromium, ruthenium, iron, manganese, nickel, antimony and palladium.Described metal-salt and part (such as amine, alkoxide etc.) thus complexing and promote to solidify with decomplexing agent activation.As an example, mention the decomplexing agent of 1-acetyl-acetanilide as the complex compound for cupric bromide (II) and N,N-DMAA.
Summary of the invention
The object of the invention is to overcome the above-mentioned shortcoming of prior art.Especially, the object of the present invention is to provide catalyzer, described catalyzer causes the improvement of following character or the coordination of following character.
The feature of described catalyzer should be high catalytic activity and the selectivity aspect urethane reaction (being the OH-group of alcohol and reacting of isocyanate groups), and can realize by polyfunctional alcohol's (polyvalent alcohol) and polyisocyanates and be promptly subject to moisture effects and build the polyether polyols with reduced unsaturation that mechanical property is high with the least possible.In addition, described catalyzer should have enough hydrolytic resistances, with conventional storage condition (be room temperature or slightly raise temperature) under within the several months, remain on containing the polyhydric alcohol composition of residual water in and without violent loss of activity.In addition, described catalyzer should reduce the thermotolerance through curing polyether polyols with reduced unsaturation as few as possible.In addition, described catalyzer should room temperature or slightly raise temperature under be liquid or in urethane parent material or softening agent excellent dissolution so that it can be used at room temperature curing solvent-free system in simple mode.Finally, described catalyzer should have alap toxicity.
Have been surprisingly found that at present the novel metal complex compound with desirable properties according to claim 1.Described novel metal complex compound has formula M k(L) x(Y) kz-nxwherein M represents z-valency metallic cation, it is selected from metallic cation and the oxygenate metallic cation of transition metal or the 13rd to 15 family's metal main group elements, k represents 1 to 20 integer, x represent 1,2,3 or 4, z represent 2,3 or 4, n represent 1,2 or 3, Y represents part with a negative charge and the part of L expression (I)
Wherein R 1and R 2represent independently of one another hydrogen base, there is the saturated or undersaturated alkyl of the monovalence of 1 to 10 carbon atom, or represent to have together the divalent alkyl of 3 to 6 carbon atoms,
R 3represent hydrogen base, there is 1 to 12 carbon atom optionally comprise heteroatomic univalent saturated hydrocarbon radical, or represent together to have 3 to 6 carbon atoms optionally comprise heteroatomic divalent alkyl, and
A represents the group of polyoxyalkylene or polyoxygenated alkylated compound, and it optionally has 1 of one or two following formula, 3-keto-amide end group
Metallic cation is preferably metallic cation or the oxygenate metallic cation of scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, aluminium, gallium, indium, germanium, tin, lead, antimony and bismuth, the particularly preferably metallic cation of lanthanum, titanium, zirconium, molybdenum, iron, zinc, tin and bismuth or oxygenate metallic cation.Very particularly preferably be two oxygenate molybdenum (VI)-positively charged ions, iron (III)-positively charged ion, zinc (II)-positively charged ion, bismuth (III)-positively charged ion and zirconium (IV)-positively charged ion because they have extra high catalytic activity and selectivity aspect urethane reaction.
At formula M according to the present invention k(L) x(Y) kz-nxmetal complex compounds in, A represents molecular-weight average M nbe preferably the group of approximately 200 to 5000g/mol, particularly preferably approximately 200 polyoxyalkylenes to 2000g/mol or polyoxygenated alkylated compound.The shortcoming that too low molecular weight has is, tend to very lowly according to the solubleness of metal complex compounds of the present invention, and that too high molecular weight causes the catalytic activity of and its every weight unit very low according to the metal content of metal complex compounds of the present invention therefore to tend to is very low.
According to formula M of the present invention k(L) x(Y) kz-nxmetal complex compounds represent to have one or more metallic cations as 1 of central atom and one or more formula (I), 3-keto-amide negatively charged ion is as the monokaryon of part or the complex compound of multinuclear, described part is bonded to central atom by the coordination of 1,3-keto-amide group and can two or three central atom of bridging in the time that n represents 2 or 3.In this case, can represent the multinuclear complex compound of k=2 to 20 according to metal complex compounds of the present invention.
Preferably, k represents 1 to 10 integer, particularly preferably 1 to 5 integer, very particularly preferably 1.In the end in a situation, be therefore monokaryon according to metal complex compounds of the present invention.It tends to have low viscosity and good solubility.
Preferably, n represents 1 or 2, because this metal complex compounds tends to have low viscosity and good solubility.
Particularly preferably be according to such metal complex compounds of the present invention, wherein k represent 1 and n represent 1, or k represent 1 and n represent 2.
It is also preferred that according to formula M of the present invention k(L) x(Y) kz-nxmetal complex compounds, wherein k represent 1, n represent 1 or 2 and M be two oxygenate molybdenum (VI)-positively charged ions, iron (III)-positively charged ion, zinc (II)-positively charged ion, bismuth (III)-positively charged ion or zirconium (IV)-positively charged ion.
Very particularly preferably be formula M k(L) x(Y) kz-nxmetal complex compounds, wherein M is iron (III)-positively charged ion, k be 1, x be 3 and kz-nx be 0; Or M is two oxygenate molybdenum (VI)-positively charged ions, k be 1, x be 2 and kz-nx be 0; Or M is zinc (II)-positively charged ion, k be 1, x be 2 and kz-nx be 0; Or M is bismuth (III)-positively charged ion, k be 1, x be 3 and kz-nx be 0; Or M is zirconium (IV)-positively charged ion, k be 1, x be 4 and kz-nx be 0.
The ligand L of formula (I) has in form by a negative charge of 1,3-keto-amide structure delocalization.Therefore it can show as different critical structures (Grenzstrukturen), for example critical structures described below.Within the scope of the invention, all possible critical structures of the ligand L of formula (I) is considered to be equivalence.
Part Y represents the part with a negative charge arbitrarily, particularly suitable organic anion, preferably carboxide, particularly preferably 1,3-dicarbapentaborane compound, for example acetylacetonate or 2,2,6,6-tetramethyl-heptane-3,5-bis-ketonates.
According to formula M of the present invention k(L) x(Y) kz-nxmetal complex compounds (thering is M as central atom and the complex bound ligand L of formula (I) and optional Y) be neutral.
The ligand L of formula (I) can be identical or different.Particularly preferably there is the ligand L of identical formula (I).
In formula (I), R 1and R 2represent independently of one another hydrogen base, there is the saturated or undersaturated alkyl of the monovalence of 1 to 10 carbon atom, or represent to have together the divalent alkyl of 3 to 6 carbon atoms.
The univalent saturated hydrocarbon radical with 1 to 10 carbon atom is preferably alkyl, particularly methyl, propyl group, sec.-propyl or the butyl with 1 to 4 carbon atom.Its advantage having is that therefore metal complex compounds tends to as liquid or excellent dissolution.The alkyl very particularly preferably, with 1 to 4 carbon atom is methyl.Described univalent unsaturated hydrocarbon radical is also preferably aryl, particularly phenyl.
Preferably, R 1and R 2form and there are 3 to 4 carbon atoms together, particularly there is the divalence methyl of 3 carbon atoms.
Particularly preferred, R 2for hydrogen base, because therefore metal complex compounds is tending towards stablizing especially.
The divalent alkyl with 3 to 6 carbon atoms is understood to formula-(CH 2) n-group, wherein n represents 3 to 6.
R 3represent hydrogen base, what have 1 to 12 carbon atom optionally comprises heteroatomic univalent saturated hydrocarbon radical, and what phenmethyl or represent together had 3 to 6 carbon atoms optionally comprises heteroatomic divalent alkyl.
The univalent saturated hydrocarbon radical with 1 to 12 carbon atom is preferably the alkyl with 1 to 8 carbon atom, is particularly preferably methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, 2-butyl or 2-ethyl-hexyl.Its advantage having is that therefore metal complex compounds tends to as liquid or excellent dissolution.
Particularly preferably, R 3represent hydrogen base, methyl or sec.-propyl.
The selection of the preferred group in the ligand L of formula (I) is preferably based on as follows: as parent material for the preparation of formula M according to the present invention k(L) x(Y) kz-nxmetal complex compounds corresponding 1,3-keto-amide can simply be prepared and/or commercially available acquisition and therefore cheap.
The invention still further relates to the method for the preparation of metal complex compounds, wherein by 1 of following formula, 3-keto-amide reacts with metal-salt or metal complex,
Wherein R 1, R 2, R 3, A and n as above define, described metal-salt or metal complex are selected from salt or the complex compound of transition metal or 13 to 15 family's metal main group elements.
Be preferably salt or the complex compound of scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, aluminium, gallium, indium, germanium, tin, lead, antimony and bismuth.Particularly preferred is salt or the complex compound of lanthanum, titanium, zirconium, molybdenum, iron, zinc, tin and bismuth.Very particularly preferably be salt or the complex compound of two oxygenate molybdenums (VI), iron (III), zinc (II), bismuth (III) and zirconium (IV).
The salt of preferred these metals is dichloride and carbonate.The complex compound of preferred these metals is dicarboxylate and 1,3-, bis-ketonates.A complex compound very particularly preferably.
Stoichiometric ratio between the salt of transition metal or 13 to 15 family's metal main group elements or complex compound and 1,3-keto-amide preferably regulates like this, and the quantity that makes 1,3-keto-amide group is at least corresponding to the price z of atoms metal.For example, preferably use for the bismuth carboxylate (III) of 1mol 3mol at least n=1 1,1 of the n=2 of 3-keto-amide or 1,5mol, 3-keto-amide.
Use 1, the 3-keto-amide preferably reaction by polyetheramine and diketene or 1,3-ketone ester obtains.
Preferred polyetheramine is polyoxyalkylene amine, preferably has approximately 200 to 5000g/mol molecular-weight average M npolyoxyalkylene amine, for example, with trade name (from Huntsman), Polyetheramine (from BASF) or PC those of (from Nitroil) commercially available acquisition.Particularly preferred type is m-600, m-1000, m-2000, m-2070, xTJ-249, xTJ-435, xTJ-436, xTJ-581, d-230, d-400, d-2000, d-4000, xTJ-582, xTJ-578, hK-511, eD-600, eD-900, eD-2003, xTJ-568, xTJ-569, xTJ-533, xTJ-536, xTJ-542, xTJ-548, xTJ-559, sD-231, sD-401, sD-2001, t-403, t-3000, t-5000, xTJ-566 and sT-404 (all from Huntsman), and from the similar type of BASF and Nitroil.Particularly preferred for thering is approximately 200 to 2000g/mol molecular-weight average M npolyoxyalkylene amine.Very particularly preferably be polyoxygenated propylidene amine, particularly polyoxygenated propylidene monoamine and polyoxygenated propylidene diamine, it optionally comprises a certain proportion of other alkylidene oxide unit, for example oxybutylene unit and be particularly oxidized ethylidene unit.Be suitable as being in particular of polyoxygenated propylidene monoamine m-600, m-1000 and xTJ-581 type.Be suitable as being in particular of polyoxygenated propylidene diamine d-230, d-400, d-2000, xTJ-582, xTJ-578, sD-231, sD-401 and sD-2001 type.
Preferred 1,3-ketone ester is Acetacetic acid alkyl ester, particularly preferably etheric acid methyl ester, etheric acid ethyl ester and etheric acid tertiary butyl ester.
Preferably, 1, being prepared as follows of 3-keto-amide carried out: preferably follow and be stirred in 100 to 500mbar, particularly preferably under about 300mbar, preferably 1 to 20 hour, particularly preferably the mixture of polyetheramine and dienone or 1,3-ketone ester is heated in approximately 4 hours to preferably 50 to 150 DEG C, the temperature of approximately 110 DEG C particularly preferably.Then preferably remove in a vacuum the volatile component in reaction mixture.
1,3-keto-amide also can be preferably as follows acquisition: preferably by dienone or 1,3-ketone ester slowly adds and is heated to preferably 80 to 160 DEG C, particularly preferably in the polyetheramine of approximately 130 DEG C, and reaction mixture is remained on to 80 to 160 DEG C, preferably at approximately 130 DEG C preferably 10 to 30 hours, particularly preferably approximately 18 hours again.Then, be preferably cooled to room temperature and preferably remove in a vacuum the volatile component in mixture.Obtained resistates is preferably dissolved in ethyl acetate, uses hydrochloric acid cleaning solution, be dried and completely concentrated with magnesium sulfate.
As mentioned above, particularly preferably use salt or the complex compound of two oxygenate molybdenums (VI), iron (III), zinc (II) and bismuth (III).
The preparation of preferred two oxygenate molybdenum (VI) complex compounds is preferably as follows to be carried out: the salt of two oxygenate molybdenums (VI) or complex compound and 1,3-keto-amide are mixed and preferably follow to be stirred in 1 to 24 hour, preferably in approximately 2 hours, mixture to be heated to 50 to 130 DEG C, the preferred temperature of approximately 80 DEG C.Then preferably remove in a vacuum the volatile component in reaction mixture.
The preparation of same preferred iron (III) complex compound is preferably as follows to be carried out: the salt or complex compound and 1 that make iron (III), 3-keto-amide mixes and preferably follows and be stirred in 1 to 24 hour, preferably in approximately 5 hours, mixture is heated to 50 to 130 DEG C, the preferred temperature of approximately 90 DEG C.Then preferably remove in a vacuum the volatile component in reaction mixture.
The preparation of same preferred zinc (II) complex compound is preferably as follows to be carried out: the salt of zinc (II) or complex compound are mixed with 1,3-keto-amide and preferably follow to be stirred in 1 to 24 hour, preferably in approximately 3 hours, mixture to be heated to the temperature of 50 to 130 DEG C, preferred approximately 90 DEG C.Then preferably remove in a vacuum the volatile component in reaction mixture.
Same preferred bismuth (III) complex compound can be preferably as follows acquisition: the salt of bismuth (III) or complex compound are mixed with 1,3-keto-amide and preferably follow to be stirred in 1 to 24 hour, preferably in approximately 2 hours, mixture to be heated to the temperature of 50 to 130 DEG C, preferred approximately 80 DEG C.Preferably, then reaction mixture is cooled to preferred room temperature.
The invention still further relates to the metal complex compounds obtaining with aforesaid method, it is such metal complex compounds, it comprises by 1 of the salt of at least one transition metal or 13 to 15 family's metal main group elements or complex compound and at least one following formula, the reaction product that 3-keto-amide forms
Wherein R 1, R 2, R 3, A and n have above-mentioned definition.
Metal complex compounds according to the present invention can be used as for curable material, preferably uses for the catalyzer of polyurethane composition.Metal complex compounds according to the present invention accelerates solidifying of curable material, and described curable material has the reactive group that can carry out crosslinking reaction.Especially, accelerate solidifying of bicomponent polyurethane composition according to metal complex compounds of the present invention, described bicomponent polyurethane composition is with himself and optionally under the impact of moisture, be cross-linked by sealing or particularly free isocyanate groups.Especially promote urethane reaction at this, i.e. reacting of the OH-group of isocyanate groups and alcohol.Treat that crosslinked composition also can comprise other and can carry out the reactive group of crosslinking reaction, for example alkoxysilane groups particularly.Preferably, alkoxysilane groups is the trialkoxysilane groups for example comprising in silane adhesive.
Can be used in bicomponent polyurethane composition preferably as catalyzer according to metal complex compounds of the present invention.Except metal complex compounds according to the present invention, bicomponent polyurethane composition also comprise polyvalent alcohol as the first component and polyisocyanates as second component.
" two-pack " represents such composition, the composition of wherein said composition is present in two different components, and described two different components are stored in container separated from one another and the stable storing of respectively doing for oneself.And then before the using of composition or just make two kinds of components be mixed with each other in the application of composition, therefore the composition through mixing solidifies, and wherein the effect of the curing temperature by moisture and/or rising is just carried out or completes in some cases.
With the material title headed by " poly-(many) ", as polyvalent alcohol or polyisocyanates, the material that on representation, per molecule comprises two or more functional groups that occur in its title.
Term " polyisocyanates " comprises the compound with two or more isocyanate groups, and no matter it is monomeric diisocyanate, oligomeric polyisocyanates or the polymkeric substance with isocyanate groups.
What be suitable as polyisocyanates is for example the polyisocyanates of following form: the oligopolymer of monomeric diisocyanate or triisocyanate or monomeric diisocyanate or the derivative of monomeric diisocyanate.
What be suitable as monomeric diisocyanate or triisocyanate is for example Isosorbide-5-Nitrae-tetramethylene-vulcabond, 2-methyl pentamethylene-1,5-vulcabond, 1,6-hexamethylene diisocyanate (HDI), 2,2,4-and 2,4,4-trimethylammonium-1,6-hexamethylene diisocyanate (TMDI), 1,10-decamethylene vulcabond, 1,12-, ten dimethylene diisocyanates, Methionin-and Methionin ester vulcabond, hexanaphthene-1,3-and-Isosorbide-5-Nitrae-vulcabond, 1-methyl-2,4-and-2, any mixture of 6-bis-isocyanatos-hexanaphthene and these isomer, 1-isocyanato-3,3,5-trimethylammonium-5-isocyanato methyl-cyclohexyl alkane (=isophorone diisocyanate or IPDI), perhydro-2,4'-and-4,4'-diphenylmethanediisocyanate (HMDI), Isosorbide-5-Nitrae-bis-isocyanato-2,2,6-trimethyl-cyclohexane (TMCDI), 1,3-and Isosorbide-5-Nitrae-bis--(isocyanato methyl)-hexanaphthene, m-and p-phenylenedimethylidyne-vulcabond (m-and p-XDI), m-and p-tetramethyl--1,3-and-Isosorbide-5-Nitrae-xylylene diisocyanate (m-and p-TMXDI), two-(1-isocyanato-1-methylethyl)-naphthalene, dimerization and three polyglycerol fatty acid isocyanic ester for example 3,6-is two-(9-isocyanato nonyl)-4,5-bis--(1-heptenyl)-tetrahydrobenzene (dimerization (Dimeryl) vulcabond), α, α, α ', α ', α ' ', α ' '-vegolysen, 3,5-Three methyl Benzene triisocyanate, the any mixture (TDI) of 2,4-and 2,6-tolylene diisocyanate and these isomer, 4,4'-, the any mixture (MDI) of 2,4'-and 2,2'-diphenylmethanediisocyanate and these isomer, the mixture of MDI and MDI-homologue (polymeric MDI or PMDI), 1,3-and Isosorbide-5-Nitrae-phenylene diisocyanate, 2,3,5,6-tetramethyl--Isosorbide-5-Nitrae-bis-isocyanato benzene, naphthalene-1,5-vulcabond (NDI), 3,3'-dimethyl-4,4'-bis-isocyanato biphenyl (TODI), dianisidine vulcabond (DADI), 1,3,5-tri--(isocyanato methyl)-benzene, three-(4-isocyanato phenyl)-methane and three-(4-isocyanato phenyl)-thiophosphatephosphorothioate.
Preferred polyisocyanates is commercially available common vulcabond.Particularly preferred is the oligopolymer of HDI, IPDI, TDI and MDI and vulcabond and the polyether polyols with reduced unsaturation (NCO-prepolymer) with isocyanate groups.
As polyvalent alcohol, can for example use following commercially available common polyvalent alcohol or its mixture:
-polyoxyalkylene polyols, be also referred to as polyether glycol or oligomeric ether alcohol, it is oxyethane, 1, 2-propylene oxide, 1, 2-or 2, 3-butylene oxide ring, trimethylene oxide, the polymerisate of tetrahydrofuran (THF) or its mixture, it may carry out polymerization by means of the starter molecules with two or more active hydrogen atoms, such as water of described starter molecules, ammonia or there are multiple OH-or the compound of NH-group, for example 1, 2-ethylene glycol, 1, 2-and 1, ammediol, neopentyl glycol, Diethylene Glycol, triethylene glycol, the dipropylene glycol of isomery and tripropylene glycol, the butyleneglycol of isomery, pentanediol, hexylene glycol, heptanediol, ethohexadiol, nonanediol, decanediol, undecane glycol, 1, 3-and 1, 4-cyclohexanedimethanol, dihydroxyphenyl propane, Hydrogenated Bisphenol A, 1, 1, 1-trimethylolethane, 1, 1, 1-TriMethylolPropane(TMP), glycerine, aniline, and the mixture of above-claimed cpd.Both can use the there is low-unsaturation-degree polyoxyalkylene polyols (for example making by means of so-called bimetallic cyanide complex catalyst (DMC-catalyzer)) of (record and provide with the milliequivalent degree of unsaturation (mEq/g) of every gram of polyvalent alcohol according to ASTM D-2849-69), also can use the polyoxyalkylene polyols (for example making as NaOH, KOH, CsOH or alkali metal alcoholates by means of anionic catalyst) with higher degree of unsaturation.
Specially suitable is polyoxyalkylene glycol or polyoxyalkylene triol, particularly polyoxygenated ethylidene and polyoxygenated trimethylene glycol and triol.Specially suitable for degree of unsaturation is less than 0.02mEq/g and polyoxyalkylene glycol and the triol of molecular weight within the scope of 1000-30000g/mol, and molecular weight be 400-8000g/mol polyoxygenated trimethylene glycol and triol.
Similarly, specially suitable is the polyoxygenated propylidene polyvalent alcohol of so-called ethylene oxide-capped (" EO-end-blocking ", ethylene oxide-capped).The latter is special polyoxygenated propylidene-polyoxygenated ethylidene polyvalent alcohol, it for example obtains by the following method: after the reaction of poly-propoxylation finishes by pure polyoxygenated propylidene polyvalent alcohol, particularly polyoxygenated trimethylene glycol and-triol oxyethane continues alkoxylate also makes it have primary hydroxyl thus.
-styrene-acrylonitrile-or the polyether glycol of vinyl cyanide-methyl methacrylate-grafted.
-polyester polyol, is also referred to as oligomer ester alcohol, and it is prepared according to currently known methods (the particularly polycondensation of the polycondensation of hydroxycarboxylic acid or aliphatic series and/or aromatics poly carboxylic acid and binary or polyvalent alcohol).
Those for preparing by binary to ternary (particularly binary) alcohol and organic dicarboxylic acid or tricarboxylic acid (particularly dicarboxylic acid) or its acid anhydrides or ester that are particularly suitable as polyester polyol, described binary to trivalent alcohol is for example ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol, neopentyl glycol, BDO, 1,5-PD, 3-methyl isophthalic acid, 5-hexylene glycol, 1,6-hexylene glycol, 1,8-ethohexadiol, decamethylene-glycol, 1,12-dodecanediol, 1,12-hydroxyl stearyl alcohol, 1,4 cyclohexane dimethanol, dimer (fatty acid) yl glycol (dimer diol), hydroxypivalic acid DOPCP, glycerine, the mixture of 1,1,1-TriMethylolPropane(TMP) or above-mentioned alcohol, described organic dicarboxylic acid or tricarboxylic acid or its acid anhydrides or ester are for example succsinic acid, pentanedioic acid, hexanodioic acid, trimethyladipic acid, suberic acid, nonane diacid, sebacic acid, dodecanedicarboxylic acid, toxilic acid, fumaric acid, dimer (fatty acid) yl, phthalic acid, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, dimethyl terephthalate, hexahydrophthalic acid, trimellitic acid and trimellitic acid 1,2-anhydride, or the mixture of above-mentioned acid, and the polyester polyol of for example being prepared by 6-caprolactone and for example above-mentioned dibasic alcohol of initiator or trivalent alcohol by lactone.
-polycarbonate polyol, for example those that obtain that react with dialkyl carbonate, diaryl carbonate or carbonyl chloride by above-mentioned (polyester polyol uses in order to build) alcohol for example.
-with the segmented copolymer of at least two hydroxyls, described segmented copolymer has the block of at least two the different polyethers with the above-mentioned type, polyester and/or polycarbonate structures, particularly polyether polyester polyvalent alcohol.
-polyacrylate polyol and polymethacrylate polyvalent alcohol.
The fat of-poly-hydroxy official energy and oily, for example natural fat and oil, particularly Viscotrol C; Or by natural fat and oil are carried out to---so-called oil chemistry---polyvalent alcohol that chemical modification obtains, for example also carry out with carboxylic acid or alcohol epoxy polyester or the epoxidized polyether that ring opening obtains subsequently by undersaturated oil being carried out to epoxidation, or the polyvalent alcohol obtaining by hydroformylation and the undersaturated oil of hydrogenation; Or by natural fat and oil by decomposition technique for example, as alcoholysis or ozone decomposed and subsequently the degradation production or derivatives thereof of acquisition like this is carried out to chemical bonding, the polyvalent alcohol obtaining by transesterify or dimerisation.Suitable natural fat and oily degradation production be lipid acid and fatty alcohol and fatty acid ester, particularly methyl ester (FAME) particularly, and it for example can and be hydrogenated to hydroxy fatty acid by hydroformylation and be derivatized and obtain.
-poly-hydrocarbon polyvalent alcohol, also referred to as oligomeric hydrocarbon polymer alcohol (Oligohydrocarbonole), for example polyolefine, polyisobutene, the polyisoprene of poly-hydroxy official energy; Ethylene-propylene-multipolymer, ethene-butylene-multipolymer or the ethylene-propylene-diene-multipolymer of poly-hydroxy official energy; Diene (particularly 1,3-butadiene) polymkeric substance of poly-hydroxy official energy, described polymkeric substance especially also can be prepared by anionoid polymerization; The diene copolymers of poly-hydroxy official energy, described diene is for example 1,3-divinyl or diene mixture and vinyl monomer for example vinylbenzene, vinyl cyanide, vinylchlorid, vinyl-acetic ester, vinyl alcohol, iso-butylene and isoprene, for example acrylonitrile/butadiene-the multipolymer of poly-hydroxy official energy, those that for example can prepare by the acrylonitrile/butadiene-multipolymer of epoxide or amino alcohol and carboxy blocking; And diene polymer or the multipolymer of the poly-hydroxy official of hydrogenation energy.
Above-mentioned polyvalent alcohol preferably has the molecular-weight average of 250-30000g/mol, particularly 400-20000g/mol, and preferably has the average OH-functionality in 1.6 to 3 scopes.
The in the situation that of oligopolymer or polymkeric substance, " molecular weight " is understood to weight-average molecular weight M all the time n.
Particularly preferably be use polyether glycol, optimization polypropylene polyvalent alcohol and polyethylene-polypropylene-polyol blend, and polyester polyol and polycarbonate polyol.
Preferably be present in the first component according to metal complex compounds of the present invention, its advantage is not affect the stability in storage (weather resistance) of the polyisocyanates of the compound sensitivity to a katalysis in second component.
Metal complex compounds according to the present invention can be used as independent catalyzer or uses together with other catalyzer, and described other catalyzer is for example bismuth compound, tin compound or zirconium compounds or tertiary amine.
Can optionally comprise other conventional auxiliary agent and additive using, such as pigment, softening agent or thinner, solidifying agent, linking agent, chain propagation agent, other catalyzer, tackiness agent, stablizer, auxiliary rheological agents and siccative etc. according to bicomponent polyurethane composition of the present invention.
Amount as elemental metals is calculated, according to metal complex compounds of the present invention preferably with the amount of 0.0002 to 1 % by weight, particularly preferably with the amount of 0.001 to 0.5 % by weight be very particularly preferably present in according in bicomponent polyurethane composition of the present invention, with the weighing scale of composition with the amount of 0.002 to 0.3 % by weight.Too high amount cause the open hour of composition or process period too short, and be that composition is crossed weakly catalyzed and therefore cross slowly, not exclusively and/or mistakenly and solidify by the shortcoming of too low amount.In bicomponent polyurethane composition according to the present invention, metal complex compounds according to the present invention accounts for 0.001 to 10, preferably 0.005 to 5 and the atoms metal of 0.01 to 3mmol-equivalent particularly preferably, in 100g composition.
In the time that metal complex compounds according to the present invention is the complex compound of two oxygenate molybdenums (VI), amount as simple substance molybdenum is calculated, according to metal complex compounds of the present invention preferably with the amount of 0.01 to 0.5 % by weight, be particularly preferably present in according in bicomponent polyurethane composition of the present invention with the amount of 0.02 to 0.3 % by weight.In bicomponent polyurethane composition according to the present invention, the complex compound of two oxygenate molybdenums (VI) is dominant and selects 0.1 to 5, the molybdenum atom of 0.2 to 3mmol-equivalent particularly preferably, in 100g composition.
In the time that metal complex compounds according to the present invention is the complex compound of iron (III) or zinc (II), amount as fe or zinc is calculated, according to metal complex compounds of the present invention preferably with the amount of 0.005 to 0.5 % by weight, be particularly preferably present in according in bicomponent polyurethane composition of the present invention with the amount of 0.01 to 0.2 % by weight.In bicomponent polyurethane composition according to the present invention, be dominant according to the complex compound of iron of the present invention (III) or zinc (II) and select 0.05 to 5, particularly preferably iron or the zinc atom of 0.1 to 2mmol-equivalent, in 100g composition.
In the time that metal complex compounds according to the present invention is the complex compound of bismuth (III), amount as bismuth with elementary is calculated, according to metal complex compounds of the present invention preferably with the amount of 0.001 to 0.2 % by weight, be particularly preferably present in according in bicomponent polyurethane composition of the present invention with the amount of 0.002 to 0.1 % by weight.In bicomponent polyurethane composition according to the present invention, be dominant according to the complex compound of bismuth of the present invention (III) and select 0.005 to 1, the bismuth atom of 0.01 to 0.5mmol-equivalent particularly preferably, in 100g composition.
As mentioned above, although its size and coenocytism, metal complex compounds according to the present invention is being quite to have activity and also quite have selectivity aspect urethane reaction.With respect to the metallic compound without 1,3-keto-amide, metal complex compounds according to the present invention is characterised in that significantly higher catalytic activity.Conventionally carry out rapidly according to solidifying of bicomponent polyurethane composition of the present invention.But the active impact not raise according to the selectivity of metal complex compounds of the present invention; Even for example, in disadvantageous condition (the high residual moisture content of high temperature, high ambient moisture or composition) lower and use and have the polyvalent alcohol or hydrophilic polyvalent alcohol of secondary OH-group, solidify and still carry out and do not form bubble.The quite thermally-stabilised and hydrolysis-stable according to metal complex compounds of the present invention, even even containing still only slowly decompose and therefore still keep its catalytic activity in the polyvalent alcohol of residual water within the longer storage time.However, use metal complex compounds according to the present invention to cause the good stability under thermal load through curing polyurethane composition.In addition, according to metal complex compounds of the present invention at room temperature for liquid and/or in softening agent or polyvalent alcohol excellent dissolution and being therefore used at room temperature curing system especially without using volatile organic solvent (VOC) in simple mode.Finally, according to formula M of the present invention k(L) x(Y) kz-nxmetal complex compounds in some compounds only for light color and cause hardly through curing polyurethane composition variable color, particularly wherein metallic cation or oxygenate metallic cation are zinc (II)-positively charged ion, bismuth (III)-positively charged ion or zirconium (IV)-cationic those compounds.Some compounds also have relatively low toxicity, and particularly wherein metallic cation or oxygenate metallic cation are two oxygenate molybdenum (VI)-positively charged ions, iron (III)-positively charged ion, zinc (II)-positively charged ion, bismuth (III)-positively charged ion or zirconium (IV)-cationic those compounds.
Can be used in many scopes according to bicomponent polyurethane composition of the present invention, for example, as the casting material of Application in Building and industrial application, sealing agent, tackiness agent, clad can, coating, paint, primer, rigid foam, soft foam, moulded piece, elastomerics, fiber, paper tinsel or film, for example, as electricity casting material, filler, gap sealing agent, cavity sealant, spackling, tackiness agent is installed, vehicle body tackiness agent, vehicle window tackiness agent, sandwich element tackiness agent, laminating adhesive, laminating adhesive, packaging adhesive, wood adhesive, parquet floor tackiness agent, anchoring adhesive, floor clad can and coating, balcony and roof coatings, concrete protective coating, parking building coating, pipeline coating, corrosion protection coating, textile coating, timber paint, fancy paint, priming paint, furniture foam, liner foam, filter foam, insulating foams, sound-proof foam, sealing foam, packaging foam, vehicle body foam, house sheet material, damper element, sealing element, tire, cylinder, bearing, roller, travelling belt, rubber thread, sole, house, window frame, implant, spongy rubber etc.
Preferred Application Areas is casting material, sealing agent, tackiness agent, clad can, coating, paint, primer, moulded piece and the elastomerics of Application in Building and industrial application.
Except bicomponent polyurethane composition, also can be used as catalyzer or promotor is for example used in, in other curable material (one-component polyurethane compositions, epoxy resin, acrylate and silicone) according to metal complex compounds of the present invention.
Embodiment
measuring method explanation
On the FT-IR of Perkin-Elmer instrument 1600, measure infrared spectra and (there is the horizontal ATR-measuring unit of ZnSe crystal; Measurement window 4000-650cm -1).Liquid sample is applied to film forming with undiluted form, solid sample is dissolved in to CH 2cl 2in.(the cm of wave number for absorption band -1) represent.
1h-NMR-spectrum is measured on Bruker DPX-300 type spectrograph under 300.13MHz; Chemical shift δ represents with ppm with respect to tetramethylsilane (TMS).Do not distinguish true coupling pattern and pseudo-coupling pattern.
(conehead is to the distance 0.05mm of plate for cone diameter 20mm, 1 ° of cone angle, and velocity of shear 0.1 is to 100s at constant temperature cone and plate viscometer Physica MCR300 for viscosity -1) on measure.
Mass spectrum (FIMS) is measured in Thermo Scientific LTQ Orbitrap XL type high resolution mass spectrometer, and the sample (100 μ g/ml) wherein with the injection speed of 10 μ l/min and the carrier of 500 μ l/min (the 1mM ammonium formiate in methyl alcohol) flow velocity, 500 μ l being dissolved in methyl alcohol directly injects mass spectrograph; By electrospray ionization (ESI +) detect.
the preparation of 1,3-keto-amide
General preparation code A
In round-bottomed flask, follow to be stirred under 300mbar, in approximately 4 hours, the mixture of polyetheramine and etheric acid tertiary butyl ester is heated to 110 DEG C.Then remove in a vacuum the volatile component in reaction mixture.
General preparation code B
Etheric acid tertiary butyl ester slowly added in the polyetheramine that is heated to 130 DEG C in round-bottomed flask and again reaction mixture remained at 130 DEG C to 18 hours.Then be cooled to room temperature and removed in a vacuum volatile component.Obtained resistates is dissolved in ethyl acetate, with hydrochloric acid soln (0.1M) cleaning solution, uses MgSO 4dry and completely concentrated.
1,3-keto-amide 1
According to general preparation code A, make 12.00g sT-404 and 12.27g etheric acid tertiary butyl ester are mixed.Obtain 17.39g reddish oil.
FT-IR:2968,2931,2871,1719,1362,1584,1443,1371,1324,1229,1216,1102,929,850,775。
1,3-keto-amide 2
According to general preparation code A, make 41.92g sD-2001 and 7.80g etheric acid tertiary butyl ester are mixed.Obtain 45.37g light yellow oil.
FT-IR:2939,2868,1737,1589,1202,1449,1371,1269,1217,1092,934,906,868,800,772。
FIMS:m/2149.52 (15), 2148.51733 (10, for the oligopolymer [MNa of x=31 +]), 2144.56 (100), and 2143.56.055 (80, for the oligopolymer [MH of x=31 +]).
1,3-keto-amide 3
According to general preparation code A, make 103.10g sD-401 and 65.13g etheric acid tertiary butyl ester are mixed.Obtain 133.90g light yellow oil.
FT-IR:2969,2929,2870,1718,1633,1584,1444,1372,1341,1208,1099,1018,928,862,773。
1,3-keto-amide 4
According to general preparation code B, make 76.50g d-230 and 130.02g etheric acid tertiary butyl ester are mixed.Obtain 51.93g light yellow oil.
FT-IR:3305,2973,2875,1714,1645,1542,1452,1410,1358,1323,1254,1147,1103,1024,922,847,668。
FIMS:m/z497.28 (90), 475.30 (54), 439.24 (43), 417.26047 (100, for the oligopolymer [MH of x=3 +]), 359.22 (41).
1,3-keto-amide 5
According to general preparation code B, make 15.76g d-400 and 14.99g etheric acid tertiary butyl ester are mixed.Obtain 13.21g light yellow oil.
FT-IR:3306,2971,2929,2869,1715,1646,1540,1453,1409,1369,1252,1143,1098,1015,924,848,775,750。
FIMS:m/z649.42 (30), 623.45 (63), 607.41339 (100, for the oligopolymer [MNH of x=6 4 +]), 591.38 (36).
1,3-keto-amide 6
According to general preparation code B, make 82.10g d-2000 and 17.14g etheric acid tertiary butyl ester are mixed.Obtain 87.77g light yellow oil.
FT-IR:3322,2969,2867,1715,1649,1535,1451,1371,1343,1296,1253,1095,1013,921,866。
1,3-keto-amide 7
According to general preparation code B, make 62.33g m-600 and 22.39g etheric acid tertiary butyl ester are mixed.Obtain 58.14g light yellow oil.
FT-IR:3323,2969,2867,1720,1649,1547,1452,1371,1342,1297,1095,1013,924,817。
FIMS:m/z655.47 (95), 641.46 (65), 597.43359 (100, for the oligopolymer [MNH of x=8 4 +]), 583.42 (54), 539.39 (100).
1,3-keto-amide 8
According to general preparation code B, make 56.15g xTJ-581 and 15.82g etheric acid tertiary butyl ester are mixed.Obtain 32.14g brown oil.
FT-IR:3324,2978,2864,1715,1668,1540,1456,1348,1275,1256,1094,946,849,760。
1,3-keto-amide 9
According to general preparation code A, make 12.72g sD-231 and 17.94g etheric acid tertiary butyl ester are mixed.Obtain 20.62g orange oil.
FT-IR:2974,2931,2872,1715,1633,1444,2362,1106,1025,934,848,774。
the preparation of catalysts for polyurethanes
General preparation code C
In round-bottomed flask, mix two (methyl ethyl diketone) two oxygenate molybdenums (VI) and make as mentioned above 1,3-keto-amide and follow to be stirred in 2 hours and mixture is heated to 80 DEG C.Then remove in a vacuum the volatile component in reaction mixture.
Embodiment 1: catalyzer Mo1
According to general preparation code C, make two (methyl ethyl diketone) two oxygenate molybdenum (VI) and the 5.67g1 of 3.24g, 3-keto-amide 1 reacts.Obtain 7.86g red glass shape solid.
FT-IR:2969,2930,2873,1717,1588,1496,1371,1333,1266,1195,1104,1028,991,931,903,776,734。
Embodiment 2: catalyzer Mo2
According to general preparation code C, make two (methyl ethyl diketone) two oxygenate molybdenum (VI) and the 5.60g1 of 3.70g, 3-keto-amide 4 reacts.Obtain 7.42g amber glass shape solid.
FT-IR:3305,2972,2930,2873,1715,1588,1514,1446,1401,1361,1267,1182,1104,1028,969,932,898,795,733,701,668。
Embodiment 3: catalyzer Mo3
According to general preparation code C, make two (methyl ethyl diketone) two oxygenate molybdenum (VI) and the 3.66g1 of 1.80g, 3-keto-amide 5 reacts.Obtain 4.46g brown oil.
FT-IR:2968,2869,1720,1626,1564,1517,1446,1401,1369,1266,1182,1092,1007,968,931,896,794,668。
Embodiment 4: catalyzer Mo4
According to general preparation code C, make two (methyl ethyl diketone) two oxygenate molybdenum (VI) and the 11.00g1 of 1.52g, 3-keto-amide 6 reacts.Obtain 11.35g green glass shape solid.
FT-IR:3307,2969,2868,1737,1629,1566,1522,1451,1371,1091,1011,934,906。
Embodiment 5: catalyzer Mo5
According to general preparation code C, make two (methyl ethyl diketone) two oxygenate molybdenum (VI) and the 13.32g1 of 2.83g, 3-keto-amide 7 reacts.Obtain 14.42g brown oil.
FT-IR:3296,2969,2870,1630,1566,1521,1450,1403,1372,1342,1268,1093,1009,967,933,904,796。
General preparation code D
In round-bottomed flask the tri acetylacetonato iron (III) of combination drying and make as mentioned above 1,3-keto-amide and follow to be stirred in 3 hours and mixture is heated to 90 DEG C.Then remove in a vacuum the volatile component in reaction mixture.
Embodiment 6: catalyst Fe 1
According to general preparation code D, make 2.65g tri acetylacetonato iron (III) and 16.54g1,3-keto-amide 7 reacts.Obtain 17.40g sorrel oil.
FT-IR:3324,2970,2868,1651,1577,1523,1450,1372,1342,1272,2097,1016,968,926,864,775,667。
Embodiment 7: catalyst Fe 2
According to general preparation code D, make 1.41g tri acetylacetonato iron (III) and 15.70g1,3-keto-amide 2 reacts.Obtain 16.17g sorrel oil.
FT-IR:2967,2865,1638,1558,1512,1456,1372,1335,1296,1095,1013,926,865,763,657。
Embodiment 8: catalyst Fe 3
According to general preparation code D, make 0.71g tri acetylacetonato iron (III) and 7.26g1,3-keto-amide 6 reacts.Obtain 7.69g sorrel oil.
FT-IR:2967,2865,1638,1558,1512,1456,1372,1335,1296,1095,1013,926,865,763,657。
Embodiment 9: catalyst Fe 4
According to general preparation code D, make 3.54g tri acetylacetonato iron (III), 3.99gN, N-dibutyl-3-oxa-heptamide and 5.32g1, the reaction of 3-keto-amide-3.Obtain 10.32g scarlet oil.
FT-IR:2957,2930,2871,1636,1556,1511,1461,1370,1331,1271,1226,1200,1102,1019,986,956,763,661。
General preparation code E
In round-bottomed flask, mix two (methyl ethyl diketone) zinc (II) hydrates (water that comprises approximately 2 equivalents) and make as mentioned above 1,3-keto-amide and follow to be stirred in 3 hours and mixture is heated to 90 DEG C.Then remove in a vacuum the volatile component in reaction mixture.
Embodiment 10: catalyst Z n1
According to general preparation code E, make two (methyl ethyl diketone) zinc (II) hydrates of 2.53g and 17.99g1,3-keto-amide 7 reacts.Obtain 18.24g light yellow oil.
FT-IR:3325,2968,2867,1652,1547,1450,1372,1341,1298,1263,1096,1015,964,925,866,782。
Embodiment 11: catalyst Z n2
According to general preparation code E, make two (methyl ethyl diketone) zinc (II) hydrates of 1.33g and 15.57g1,3-keto-amide 2 reacts.Obtain 16.15g light yellow oil.
FT-IR:2969,2930,2866,1718,1637,1587,1517,1450,1372,1341,1296,1259,1094,1014,925,866,768。
Embodiment 12: catalyst Z n3
According to general preparation code E, make two (methyl ethyl diketone) zinc (II) hydrates of 1.31g and 9.04g1,3-keto-amide 3 reacts.Obtain 9.49g light yellow oil.
FT-IR:2968,2927,2874,1717,1634,1579,1513,1444,1372,1333,1258,1199,1100,1017,927,859,769。
Embodiment 13: catalyst Z n4
According to general preparation code E, make two (methyl ethyl diketone) zinc (II) hydrates of 0.86g and 9.77g1,3-keto-amide 8 reacts.Obtain the light brown oil of 9.88g.
FT-IR:3325,2865,1712,1666,1585,1546,1451,1348,1251,1095,995,947,849,780。
General preparation code F
In round-bottomed flask, be blended in neodecanoic acid 83 (three (neodecanoic acid) bismuth (III)) (16%Bi; From ) and make as mentioned above 1,3-keto-amide and follow to be stirred in 2 hours and mixture is heated to 80 DEG C.Then reaction mixture is cooled to room temperature.
Embodiment 14: catalyst B i1
According to general preparation code F, make 1.51g 83 and 3.98g1,3-keto-amide 2 reacts.Obtain 5.48g light yellow oil.
FT-IR:2967,2929,2867,1721,1636,1609,1539,1458,1372,1342,1296,1253,1097,1013,926,867。
Embodiment 15: catalyst B i2
According to general preparation code F, make 2.76g 83 and 1.40g1,3-keto-amide 4 reacts.Obtain 4.16g light yellow oil.
FT-IR:3330,2959,2931,2874,1698,1636,1544,1460,1360,1254,1156,1108,1015,908,817,741。
Embodiment 16: catalyst B i3
According to general preparation code F, make 1.38g 83 and 2.18g1,3-keto-amide 3 reacts.Obtain 3.56g light yellow oil.
FT-IR:2964,2932,2873,1717,1635,1602,1459,1372,1341,1102,1021,928,817,772。
Embodiment 17: catalyst B i4
According to general preparation code F, make 1.45g 83 and 1.39g1,3-keto-amide 4 reacts.Obtain 2.84g light yellow oil.
FT-IR:3304,2962,2932,2872,1714,1644,1545,1458,1359,1253,1153,1106,1022,923,817,741。
General preparation code G
(70% in propyl alcohol in round-bottomed flask, to mix propyl alcohol zirconium (IV) solution; Make 19.5%Zr) and as mentioned above 1,3-keto-amide and at room temperature stirring 3 hours.Then reaction mixture is heated to 60 DEG C and remove portion volatile component in a vacuum.
Embodiment 36: catalyst Z r1
According to general preparation code G, make 1.28g propyl alcohol zirconium (IV) solution and 13.54g1,3-keto-amide 3 reacts.Obtain the light yellow oil of 14.70g thickness.
FT-IR:2970,2931,2871,1717,1635,1568,1516,1445,1372,1333,1257,1202,1100,1018,989,963,928,861,764,740,721,668。
Embodiment 37: catalyst Z r2
According to general preparation code G, make 2.05g propyl alcohol zirconium (IV) solution and 30.66g1,3-keto-amide 2 reacts.Obtain the orange oil of 31.27g thickness.
FT-IR:2970,2930,2867,1718,1640,1568,1517,1455,1372,1339,1297,1267,1100,1013,990,864,925,866,834,764,668。
Embodiment 38: catalyst Z r3
According to general preparation code G, make 1.42g propyl alcohol zirconium (IV) solution and 9.86g1,3-keto-amide 9 reacts.Obtain the light yellow oil of 10.04g thickness.
bicomponent polyurethane composition
Embodiment 18 to 21 and 39 and Comparative Example V 1 are to V5
In order to prepare the first component, for each embodiment at centrifugal mixer (SpeedMixer tMdAC150, FlackTek Inc.) in 30 seconds with 3000U/min closely mix according to the polyether triol of table 1 ( cP4755, from Dow) and catalyzer.Then the first component of the fresh preparation of a part is filled in the aluminum pipe of interior japanning, at 60 DEG C, stores 7 days by described aluminum pipe gas-tight seal and in air circulating oven.
For each embodiment, using the first component of the fresh preparation of remainder in this way with according to table 1 as second component through modification, be at room temperature liquid diphenylmethanediisocyanate ( cD-L, from Bayer) be mixed to form polyurethane composition.
Similarly, for each embodiment, will at 60 DEG C, store first component of 7 days and be mixed to form polyurethane composition according to the second component of table 1 in an identical manner.
Test polyurethane composition aspect outward appearance, inviscid time, bubble formation and Xiao A hardness, particularly not only test has the composition of the first component of fresh preparation but also test and has the composition of the first component that stores 7 days at 60 DEG C in each case.Then in tension test, only measure the mechanical properties of composition of first component with fresh preparation, specifically for before accelerating different storage that sample is aging and afterwards.
The only outward appearance by visual assessment composition and be evaluated as " limpid ", " muddiness " or inhomogeneous (" inh. ").
For determine inviscid between (skinning time), the composition under room temperature is applied on clamp paper and at standard climate (" NK " with the layer thickness of about 3mm; 23 ± 1 DEG C, 50 ± 5% relative air humidities) under determine respectively when touch by LDPE transfer pipet on composition surface time shift liquid pipe, no longer leave over resistates first before duration.
According to the amount of going through the bubble that definite composition of skinning time produces in its solidification process, by visual assessment (" many ", " some ", " nothing ") bubble formation situation.
Be under standard climate to solidify on the test sample of 7 days and determine Xiao A hardness according to DIN53505.
In order to determine mechanical properties in tension test, prepare by composition the film that about 3mm is thick, wherein composition is cast in flat PTFE-mould and under standard climate and solidifies 7 days.Obtain inviscid and elastic film.From film, stamping out length is the dumbbell body that the long 30mm of being of 75mm, width and fabric width are 4mm, tests its a part of tensile strength, extension at break and E-modulus (under 0.5 to 5.0% elongation) according to DIN EN53504 with the draw speed of 200mm/min.The dumbbell body of remainder stores 1 day at 100 DEG C in air circulating oven, or (40 DEG C and 100% relative air humidity) stores 10 days under " poultice condition (Kataplasma) ", or under " poultice condition ", store 10 days and at 100 DEG C, store 1 day, then under standard climate, keep 1 day respectively and test as described according to DIN EN53504.
Test result is presented in table 2.
Known by table 2, the bicomponent polyurethane composition with catalyst according to the invention is limpid, uniform mixture, its before storing with all there is afterwards the relative short skinning time, and can bubble-freely solidify to form the material with relatively high intensity and well tolerable property.
Embodiment 22 to 41
As described in embodiment 18, in order to prepare the first component, respectively by polyether triol ( cP4755, from Dow) and according to the catalyst mix of table 3.Then the first component of the fresh preparation of a part is filled in the aluminum pipe of interior japanning, at 60 DEG C, stores 7 days by described aluminum pipe gas-tight seal and in air circulating oven.
For each embodiment, by the first component of the fresh preparation of remainder taking to mode described in embodiment 18 with according to table 3 as second component through modification, at room temperature as the diphenylmethanediisocyanate of liquid ( cD-L, from Bayer) be mixed to form polyurethane composition.
Similarly, for each embodiment, will at 60 DEG C, store first component of 7 days and be mixed to form polyurethane composition according to the second component of table 3 in an identical manner.
As described in to embodiment 18, test the outward appearance of polyurethane composition, inviscid time, bubble formation, Xiao A hardness and the mechanical properties in tension test.
Test result is presented in table 4.
Known by table 4, the bicomponent polyurethane composition with catalyst according to the invention is limpid, uniform mixture, its before storing with all there is afterwards the relative short skinning time, and substantially bubble-freely solidify to form the material with good Xiao A hardness.

Claims (15)

1. formula M k(L) x(Y) kz-nxmetal complex compounds, wherein M represents z-valency metallic cation, it is selected from metallic cation and the oxygenate metallic cation of transition metal or the 13rd to 15 family's metal main group elements, k represents 1 to 20 integer, x represent 1,2,3 or 4, z represent 2,3 or 4, n represent 1,2 or 3, Y represents part with a negative charge and the part of L expression (I)
Wherein R 1and R 2represent independently of one another hydrogen base, there is the saturated or unsaturated alkyl of the monovalence of 1 to 10 carbon atom, or represent to have together the divalent alkyl of 3 to 6 carbon atoms,
R 3represent hydrogen base, there is 1 to 12 carbon atom optionally comprise heteroatomic univalent saturated hydrocarbon radical, or represent together to have 3 to 6 carbon atoms optionally comprise heteroatomic divalent alkyl, and
A represents the group of polyoxyalkylene or polyoxygenated alkylated compound, and it optionally has 1 of one or two following formula, 3-keto-amide end group
2. metal complex compounds according to claim 1, wherein metallic cation is metallic cation or the oxygenate metallic cation of scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, aluminium, gallium, indium, germanium, tin, lead, antimony and bismuth, preferably metallic cation or the oxygenate metallic cation of lanthanum, titanium, zirconium, molybdenum, iron, zinc, tin or bismuth.
3. according at least one described metal complex compounds of aforementioned claim, wherein metallic cation or oxygenate metallic cation are two oxygenate molybdenum (VI)-positively charged ions, iron (III)-positively charged ion, zinc (II)-positively charged ion, bismuth (III)-positively charged ion or zirconium (IV)-positively charged ion.
4. according at least one described metal complex compounds of aforementioned claim, wherein R 1represent to have the alkyl of 1 to 4 carbon atom, preferable methyl, or phenyl.
5. according at least one described metal complex compounds of aforementioned claim, wherein R 2represent hydrogen base.
6. according at least one described metal complex compounds of aforementioned claim, wherein R 3represent hydrogen base, there is the alkyl of 1 to 8 carbon atom, preferably hydrogen base, methyl or sec.-propyl, or phenmethyl.
7. according at least one described metal complex compounds of aforementioned claim, wherein A represents molecular-weight average M nfor approximately 200 to 5000g/mol, the preferred group of approximately 200 polyoxyalkylenes to 2000g/mol or polyoxygenated alkylated compound.
8. according at least one described metal complex compounds of aforementioned claim, wherein n represents 1 or 2.
9. for the preparation of the method for metal complex compounds, wherein by 1 of following formula, 3-keto-amide reacts with metal-salt or metal complex
Wherein R 1, R 2, R 3, A and n as above define, described metal-salt or metal complex are selected from salt or the complex compound of transition metal or the 13rd to 15 family's metal main group elements, preferably scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, aluminium, gallium, indium, germanium, tin, plumbous, the salt of antimony or bismuth or complex compound, particularly preferably lanthanum, titanium, zirconium, molybdenum, iron, zinc, the salt of tin or bismuth or complex compound, very particularly preferably with two oxygenate molybdenums (VI), iron (III), zinc (II), the salt of bismuth (III) or zirconium (IV) or complex compound reaction.
10. method according to claim 9, is wherein used muriate, carbonate, carboxylate salt or 1,3-, bis-ketonates as salt or complex compound.
11. by the metal complex compounds obtaining according at least one method described in claim 9 and 10 any one.
12. according to aforementioned claim 1 to 8 and 11 at least one described metal complex compounds as for curable material, especially for the purposes of the catalyzer of polyurethane composition.
13. bicomponent polyurethane compositions, described bicomponent polyurethane composition comprises at least one polyvalent alcohol, preferred, polyethers polyvalent alcohol as the first component, and at least one polyisocyanates, preferably vulcabond is as second component with at least one is according to claim 1 to 8 and 11 at least one described metal complex compounds.
14. bicomponent polyurethane compositions according to claim 13, wherein metal complex compounds is included in the first component.
15. according to claim 13 and 14 at least one described bicomponent polyurethane compositions casting material, sealing agent, tackiness agent, clad can, coating, paint, primer, moulded piece, the elastomeric purposes as Application in Building and industrial application.
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